Methods for treating textile materials and resulting products



United States Patent 3,100,135 METHODS FOR TREATING TEXTILE MATERIALS AND RESULTING PRODUCTS Fred H. Sexsmith, Highland Park, N .J assign'or, by

mesne assignments, to Johnson & Johnson, New Brunswick, N.J., a corporation of New Jersey No Drawing. Filed Sept. 28, 1959, Ser. No. 342,596

16 Claims. (Cl. 8-116) The present invention relates to methods of treating textile materials to render them substantially shrinkproof and dimensionally stable; to the textile treating compositions used in such materials; to methods of preparing such textile treating compositions; and to the resulting dimensionally-stable textile materials possessing reduced shrinkage characteristics. More particularly, the present invention is concerned with methods of treating textile materials containing cellulosic fibers with acetal and/ or hemiacetal condensation products whereby dimensional stability of the cellulosic textile materials is obtained.

It is well known in the textile industry to treat cellulosic textile materials with Water-soluble urea-formaldehyde and melamine-formaldehyde condensates in the presence of acidic catalysts to stabilize the treated cellulosic materials against progressive dimensional shrinkage due to launderings and washings. Although reasonably satisfactory for such purposes and generally acceptable to the trade, there are many shortcomings to such use of these urea-formaldehyde and melamine-formaldehyde condensates. Among such shortcomings are: the develop ment of persistent odors in the treated materials; the creation of chlorine-retentive properties and resulting chlorine damage; subsequent yellowing and discoloring; tendering and embrittlement; and general loss in the tearing and breaking tensile strengths of the fabric.

Acetals, the reaction products of alcohols or :glycols with aldehydes, have also been employed in such shrinkproofing uses and have found moderate success. However, many individual acetals have been found unsatisfactory for many reasons. For example, efforts to react formaldehyde with pentaerythritol directly or by the usual procedures have been relatively unsuccessful due to the diifioulty of dissolving the pentaerythritol in the formaldehyde, or preventing subsequent recrystallization thereof, if dissolution of the pentaerythritol is obtained by prolonged heating. As another example, chloral (which many do not consider an aldehyde, even though it contains an aldehyde group and shows some of the reactions of an aldehyde) has been reacted with pentaerythritol but the relative water insolubil-ity of the resultant reaction product has discouraged further investigation thereof for textile purposes.

It has now been surprisingly discovered that, if pentaerythritol is reacted substantially simultaneously with formaldehyde and chloral in certain proportions, an exothermic reaction takes place without any difficulty in dissolving the pentaerythritol to yield a reaction product which can be applied to cellulosic textile materials to render them substantially shrinkproof and dimensionally stable. It has further been discovered that, the proportions of the formaldehyde and chloral are varied with respect to each other and to the pentaerythritol, the solubility of the resulting reaction product may be varied from excellent water solubility to limited water solubility, as well as from limited organic solvent solubility to excellent organic solvent solubility.

The proportions of the chloral, pentaerythritol and formaldehyde in the reaction mixture are fairly critical and for each mole of pentaerythritol, there must be at least from about 4 mole to about 3% moles of chloral and at least from about /1 mole to about 3% moles of formaldehyde. The lower limits of these ranges are critical;

smaller amounts cannot be satisfactorily commercially used. The upper limits of these ranges are not as critical and amounts in excess of those indicated may be used. For example, from about mole up to about 6 moles of chloral and from about mole up to about 6 moles of formaldehyde per mole of pentaerythritol may be used but it must be realized that such excessive molar amounts cannot ordinarily react completely with the pentaerythritol which can ordinarily react with up to a total of 4 moles of aldehydic compounds and that such excessive amounts usually affect only reaction conditions and mechanisms.

As a matter of fact, however, as will be explained in greater detail later, less than 4 moles of chloral and formaldehyde combined may react with all 4 available hydroxy radicals of pentaerythritol, under certain conditions.

Additionally, as a general rule of thumb, the greater the proportion of formaldehyde, with respect to chloral, the greater is the water solubility, and the greater the proportion of chloral, with respect to formaldehyde, the greater is the organic solvent solubility.

Chloral is commercially available as a colorless liquid having a boiling point of about C. It is used in this form rather than in the crystalline chloral hydrate form inasmuch as the additional molecule of water in the hydrate decreases its reactivity.

The pentaerythritol is used in its commercial crystalline form in the purity desired or required for the particular product.

The formaldehyde is used either as formalin (37% U.S.P. aqueous formaldehyde solution) or in the commercially available 37%, 45% and 50% low methanol forms. Paraformaldehyde or polyoxymethylene (CH O) or other more concentrated formaldehyde-yielding compounds may also be used advantageously to reduce the water content of the final preparation.

The crystalline pentaerythritol may be dispersed in the chloral with stirring. The formaldehyde, preferably as formalin, is then slowly added whereby a severely exothermic reaction ensues. The pentaerythritol rapidly goes into solution. A pale amber to clear yellow, viscous liquid results having an odor of formaldehyde but with substantially no odor of chloral, unless an excess thereof has been used. It is stable and water soluble. If desired and in many instances it has been found preferable, paraformaldehyde and pentaerythr-itol may be slurried in formalin and heated to dissolution. The chloral may then be added, 'whereat the exothermic reaction takes place, as described previously.

It is believed that acetal and/or hemiacetal formation has taken place and that the most probable final reaction product has the following structural formula:

wherein X may have an average numerical value of from about A to about 3%; Y may have an average numerical value of from about A to about 3%; Z may have an average numerical value of from 0 to about l; with the sum of X and Y having an average numerical value of from about 3 to about 4, or preferably slightly under 4 but not over 4, depending on reaction conditions.

Within the more commercial textile aspects of the present invention, however, X may have an average numerical value of from about A to about 1 /2; Y may have an average numerical value of from about 3% to about 2 /2; Z may have a very small, substantially negligible numerical value; and the sum of X and Y may have an average numerical value of 4, or slightly thereunder but not thereover. Such products will tend to be more water soluble and are better suited for textile uses.

It is not essential that there be a total of four moles of chloral and formaldehyde for each mole of pentaerythritol in order that all four hydroxy groups of the pentaerythritol enter into the acetal, or more precisely speaking, the hemiacetal formation reaction. It is quite possible, depending upon the proportions of the chloral and formaldehyde to eachother and to the pentaerythritol and upon the amount of water prment in the aqueous re action mixture, for one mole of an aldehydic compound to react with two hydroxy groups of the pentaerythritol to form an internal acetal having, for example, the following structural formula:

O CH: GHzO wherein A may have an average numerical value of from to about 1%; B may have an average numerical value of from about A to about 2; C may have an average numerical value of from 0 to about 1; with the sum of A and B having an average numerical value of from about 1 to about 2, or preferably slightly under 2, but not over 2.

In another possible variation, similarly depending upon the proportions of the chloral, pentaerythritol and formaldehyde and upon the amount of water present in the aqueous reaction mixture, and in this case particularly upon the amount of formaldehyde present, one obtains compounds falling under the folowing structural formula:

-OCH2 GHzO-GHz-OCH: C1120- wherein D may have an average numerical value of from to about 4; B may have an average numerical value of from 0 to about 3%; F may have an average numerical value of from 0 to about 1; and the sum of D and E may have an average numerical value of from about 3 to about 4, or preferably slightly under 4, but not over 4.

The amount of the textile treating composition which is applied to the textile material may be varied within rela-.

tively wide limits, depending primarily upon the textile properties and characteristics desired or required. Percent Wet pick-ups by the textile material of the textile treating composition of from about 50% to about 200% based on the weight of the textile material have been found satisfactory, with a range of from about 90% to about 160% being preferred. Percent dry add-ons (after drying) of from about 1% to about 30% based on the weight of the textile material have been found satisfactory, with a range of from about 5% to about 25% being preferred, with the most economical range extending from about to about Amounts greater than 30% or-less. than 1% may be applied to the textile materials for special purposes but such is normally neither desired nor required.

lnasmuoh as the textile treating agent is basically the reactive" type which chemically reacts with the cellulose molecule, increased Weights of treating agent will be required when greater proportions of chloral are used with lesser proportions of formaldehyde, due to the greater molecular weight of chloral as compared to the lesser molecular weight of the formaldehyde.

The concentration of the ohloral-pentaerythritol-formaldehyde condensate in the textile treating composition may also be varied within relatively wide limits. Concentrations of from about 2% to about have been found satisfactory with a range of from about 5% to about 16%. being preferred. Concentrations greater than 25% may be used but are sometimes more diflicult to handle and apply. Concentrations less than 2% may be used for special purposes when it is desired to apply only small amounts of the treating agent.

The textile treating composition is preferably applied to the textile materials in an aqueous solution or dispersion, although, where circumstances require it, other solvent media or even organic solvent media may be employed. The textile treating composition may be applied to the textile materials by various methods and by means of various apparatus now well known in industry. For example, the textile treating composition may be applied by spraying, immersion, or by contact, either with or without the assistance of padding, nip or squeeze rolls or other types of extracting equipment. Inasmuch as a wide choice may be made in the relative proportions and concentrations of the constituents of the textile treating composition, it is possible to use all types of coating and impregnating apparatus in applying the treating compositions to the textile materials.

The textile materials to be treated by the textile treating compositions of the present invention are preferably woven. Within the broader aspects of the present invention, however, the textile treating compositions may be applied to any type of textile material including fabrics which are nonwoven, knitted, crocheted, felted, braided or the like.

Subsequent to the application of the textile treating composition to the textile materials, the treated materials may be first dried at elevated temperatures of from about C. ('176 F.) to about C. (248 F). The applied textile treating composition is then cured at temperatures of from about C. (275 F.) to about 180 C. (356 F.) for a period of from about /2 minute to about 6 minutes. If desired, the drying and curing may be accomplished in one step. Curing catalysts known to the art, such as magnesium chloride or zinc nitrate, are used and are preferably included in the texrtile treating composition and applied therewith to the textile materials. The heating should be suflioient to bring about the required reaction between the chloralpentaerythri-tol-formaldehyde reaction product and the cellulosic fibers in the treated textile materials whereby the fibers are chemically modified and exhibit difierent physical properties and characteristics.

If desired, other additives or improvement agents may be included with the textile treating composition during its preparation and application. For example, such other additives may include binders, dyes, pigments, flame retardants, softeners, mothand mildew-proofing agents, Wet strength improvers, insecticides, germicides, disinfeotants, etc.

The textile materials which are treated by the composition of the present invention are preferably cellulosic; natural oellulosic materials such as cotton, flax, hemp, sisal, jute, etc., or synthetic or man-made cellulosic materials such as regenerated cellulose obtained by the visoose, cuprammonium or saponification methods being preferred. Blends of cellulosic fibers with non-oellulosic fibers may be used in substantially any desired proportions, say, as low as about 20% up to about 95% by Weight of the cellulosic fibers, to fabricate materials of applicability to the present invention. Other fibers suitable for such blending purposes are polyamides, such as nylon 6 and nylon 66; polyester fibers such as Dacron and Terylene; acrylic fibers such as Acrilarf and Orlon; vinyl fibers such as Dynel and Vinyon; etc.

The invention will be further illustrated in greater detail by the following specific examples. It should be understood, however, that although these examples may describe in particular detail some of the more specific features of the invention, they are given primarily for purposes of illustration and the invention in its broader aspects is not to be construed as limited thereto. All percentages and parts referred to herein and in other pontions of the specification and claims are by weight, unless specifically indicated otherwise.

Example I 350 grams of crystal-line pentaerythritol is dispersed with stirring in 1000 grams of chloral at room temperature. No formaldehyde is included. 1000 cc. of water is slowly added and a violent exothermic reaction results. The pentaerythritol rapidly dissolves. About 10 grams of 28% ammonia is added to bring the pH to -6. The solution is allowed to stand overnight. The reaction product is pale amber colored, water immiscible, stable and highly viscous (about 2000 cps. viscosity). There is some tendency to crystallization. The complete water immiscibility in substantially all proportions militates against further textile usages primarily due to the difficulty of handling and applying the treating material.

Example II 100 grams of crystalline pentaerythritol is slurried with stirring in 270 grams of 37% formalin at room tem perature. No chloral is added. No reaction takes place and the crystalline pentaerythritol does not go into solution. The slurry is then heated to the boiling point and maintained at that temperature for five minutes. The pentaerythritol finally dissolves. However, on cooling to room temperature, the pentaerythritol crystallizes out of solution. The recrystallized pentaerythritol is redissolved by reheating as before but again crystallizes out on cooling. This limited solubility militates against further textile usage due primarily to the difiiculty of handling and applying the treating agent.

Example III and formaldehyde and is believed to have the following formula:

HOCHr-OCE: CHzO-CHOH-CCla H0 OH2O our onlo-onono on This reaction product is referred to in this example as CPF. When used elsewhere in a generic sense, as will be clear from a consideration of its meaning in the text, the term CPF is intended to cover any and all re action products of chloral, pentaerythritol, and formaldehyde reacted in various proportions and under conditions described herein.

150 grams of the reaction product CPF of this example is dissolved in 850 grams of water; 20 grams of Triton X-lOO, a polyethylene glycol alkyl aryl ether emulsifier; grams of Tween 20, a sorbitan monolaurate polyoxyalkylene derivative emulsifier; 20 grams of Arquad 1845, a quaternary ammonium emulsifier; and grams of a magnesium chloride catalyst. Ignoring the added emulsifiers and catalyst, this is equivalent to almost a 15% concentration of CPF.

A 4 x 1 piece of bleached woven cotton fabric gauze) weighing 5.50 yards per pound is treated with the CPF and wrung out to a wet pick-up of about 100% by weight, based on the weight of bleached cotton fabric. The treated cotton fabric is dried in an oven at 250 F. for 5 minutes to a dry add-on of about 15% and cured at 315 F. for 3 minutes. The treated fabric and a comparison untreated woven fabric are measured (100 cm.) and marked (warp direction) and then laundered together in a conventional home automatic washing machine. The treated fabric sample still measures 100 cm. and shows no apparent shrinkage. The untreated fabric sample measures only 95.5 cms., a shrinkage of 4 /2%.

Examples IV, V, VI and VII The procedures of Example III are repeated substantially as set forth therein with the exception that the molar proportions of the chloral, pentaerythritol and formaldehyde are as follows:

Example Chloral Pentaeryth- Formalderitol hyde 15% aqueous solutions are prepared of the resulting reaction products and applied wet pick-up and about 15 dry add-on) to cotton fabrics. Heating, drying and curing follow. Substantially no shrinkage is encountered in the treated fabric samples whereas untreated fabric shrinkages average about 5% shrinkage.

Examples VIII, IX, X and XI The procedures of Example III are followed substantially as set forth therein with the exception that fabrics containing the following fibers are used:

Example Fibers 100% viscose rayon staple.

50% viscose rayon staple 50% cotton. 100% flax (linen).

75% cotton, 25% nylon 66.

The results are comparable to those obtained in Example III.

Example XII The procedures of Example III are followed substantially as set forth therein except that five test aqueous solutions of the same CPF are prepared in differing concentrations. These solutions are applied to 5 .50 bleached These tests are compared to tests made on similar fabrics with the same concentrations of an acetal shrinkproofing agent now in public use and sale.

Percent reactant Percent shrinkln comparison image, warp direcpregnant solution tion, after single laundering cycle 1 Control.

The superiority of the invention irnpregnant solution is quickly noted in that the percent shrinkage in the warp direction is quickly reduced to Zeno whereas in the comparison solution the percent shrinkage is reduced only to 1.1% and then rapidly rises thereafter to 3.3% and appears to be headed toward higher and higher shrinking percentages.

7 Example XIII The procedures of Example III are followed substantially as set forth therein except that the woven material is replaced with a viscose bonded 100% staple r-ayon nonwoven fabric weighing 550 grains per square yard. The uonwoven fabric is rendered dimensionally stable.

Example XIV A chloral (1 mole), pentaerythritol (4 moles), formaldehyde (12 moles) condensate is prepared according to the procedures set forth in Example III. 10% aqueous solutions are applied (100% wet pick-up) toseveral samples of 8.60 bleached cotton fabrics. Drying takes place at 250 F. for 5 minutes and curing takes place at 325 F. for 2 /2 minutes. Magnesium chloride (10%, based on weight of CPF), is the curing catalyst. The wash-wear properties (average) are determined (3 hot Bendix wash cycles):

Discoloration is virtually m'l; there is substantially no stifiening of the fabric; commercial acceptance is indicated. No toxicological hazards are detected.

Example XV A chloral (3 moles), pentaerythritol (8 moles), formaldehyde (29 moles) condensate is prepared according to the procedures set forth in Example III.

A clear viscous liquid is obtained after filtering; its pH is about 5: its specific gravity of room temperature is about 1.3; and its color, as measured on the standard Gardner-Holdt scale, is about 2. It possesses a slightly formaldehydic odor. Upon the addition of about 80 parts of water to about 100 parts of the CPF (38-29), the clear viscous liquid becomes cloudy, indicating that the cloud point is reached. Additional water causes an emulsion-like appearance and ultimately a small oily precipitate.

The surface tension is about 28.3 dynes per square centimeter as measured at room temperature on aDe Nuoy tensiometer; the viscosity, as measured at room temperature on a Brookfield viscosimeter, using a #3 spindle at 30 r.p.m., is about 576 centipoises. The viscosity is also measured at room temperature at 6, l2 and 60 rpm. and is substantially Newtonian.

A 10% aqueous solution (4% MgCl -6H O) is applied to 8.60 bleached cotton fabric. Drying takes place at 250 F. for 5 minutes and curing takes place at 325 F. for 2 /2 minutes. The washwear properties are determined (3 hot Bendix wash cycles):

Monsanto wrinkle re- Warp covery, degrees shrink- Material age, Drip dried appearance percent Orig- Washed incl Treated sample. 124 118 2.1 God,donly slightly corrugate Untreated con- 84 92 5. Poor, badly corrugated.

control.

Another sample is given 3 hot Bendix washes and one hand washing. Its appearance is good-very slightly corrugated. Both treated sample fabrics are well suited for diaper'materia'l wherein anti-corrugation on laundering is a very desired feature.

Although several specific examples of the inventive concept have been described, the same should not be construed as limited thereby nor to the specific features mentioned therein but to include various other equivalent features .as set forth in the claims appended hereto. It is understood that any suitable changes, modifications and variations may be made without departing from the spirit and scope of the invention.

What is claimed is:

1. A water-soluble reaction product of chloral, pentaerythritol andformaldehyde wherein the molar proportions of the reactants are in a ratio of from about /4 to about 6 mols of chloral: 1 mol of pentaerythritol: about A to about 6 molsv of formaldehyde.

2. A water-soluble reaction product of chloral, pentaerythritol and formaldehyde wherein the molar proportions of the reactants are in a ratio of from about M4 to about 3% mols of chloral: 1 mol of pentaeryt-hritokabout 3% to about 1 mol of formaldehyde.

3. A water-soluble reaction product of chloral, pentaerythritol and formaldehyde wherein the molar proportions of the reactants are in a ratio of from about A to about 1%. mols of chloralzl mol of pentaerythritolzabout 3% to about 2 /2 mols of formaldehyde.

4. A method of treating textile materials containing cellulosic fibers to render the textile materials dimensionally stable after washing which comprises: applying to said textile materials from about 50% to about200% wet pick-up weight, based on the dry weight of the textile materials, of an aqueous solution comprising from about 2% to about 25% by weight of a reaction product of chloral, pentaerytbritol and formaldehyde wherein the molar proportions of the reactants are in the ratio of from about A to 6 mols of chloralzl mol of pentaerythritolzabout 6 to mols of formaldehyde; and drying said treated textile materials whereby from about 1% to about 30%, dry weight, based on the dry weight of the textile material, remains thereon.

5. A method of treating textile materials containing cellulosic fibers to render the textile materials dimensionally stable after washing which comprises: applying to said textile materials from about to about Wet pick-up weight, based on the dry weight of the textile materials, of an aqueous solution comprising from about 5% to about 16% by weight of a reaction product of chloral, pentaerythritol and formaldehyde wherein the molar proportions of the reactants are in the ratio of from about A to 3% mols of chloralzl mol of penta erythritolvabout 3% to 1 mols of rformaldehyde; and drying said treated textile materials whereby from about 5% to about 25%, dry weight, based on the dry weight of the tetxile materials remains thereon.

6. A method of treating textile materials containing cellulosic fibers to render the textile materials dimensionally stable after Washing which comprises: applying to said textile materials from about 50% to about 200% wet pick-up weight, based on the dry weight of the textile materials, of an aqueous solution comprising from about 2% to about 25% by weight of a reaction product of chloral, pent-aerythritol and formaldehyde wherein the molar proportions of the reactants are in the ratio of from about A to 6 mols of chloralzl mol of pentaerythritoltabout 6 to mols of formaldehyde; drying said treated textile materials whereby from about 1% to about 30% dry weight, based on the dry weight of the textile material remains thereon; and reacting said reaction product, in situ with said textile materials.

7. A method of treating textile materials containing cellulosic fibers to render the textile materials dimensional- 1y stable after washing which comprises: applying to said textile materials from about 90% to about 160% wet pickup weight, based on the dry weight of the textile materials, of an aqueous solution comprising from about 5% to about 16% by weight of a reaction product of chloral, pentaerythritol and formaldehyde wherein the molar proportions of the reactants are in the ratio of from about A to 3% mols of chloral:1 mol of pentaerythritohabout 3% to 1 mols of formaldehyde; drying said treated textile materials whereby from about 5% to about 25%, dry weight, based on the dry weight of the textile material remains thereon; and reacting said reaction product, in sit-u, with said textile materials.

8. A water-soluble reaction product (of chloral, pentaerythritol and formaldehyde wherein the molar proportions of the reactants are in a ratio of from about A t 3% mols of chloral:1 mol of pentaerythritolzabout 3% to 1 mols of formaldehyde, and the total mols of chloral and formaldehyde per mol of pent-aerythritol are not greater than 4.

9. A water-soluble reaction product of chloral, pentaerythritol and formaldehyde wherein the molar proportions of the reactants are in a ratio of from about A to 1 /2 mols of chloralzl mol of pentaerythritolzabout 3% to 2 /2 moles of formaldehyde, and the total mols of chloral and formaldehyde per mol of pentaerythrito-l are not greater than 4.

10. Dimensionally stable textile materials containing cellulosic fibers cross-linked with from about 1% to 30%, dry weight based on the dry weight of the textile materials, of a textile treating composition comprising a reaction product of chloral, pentaerythritol and formaldehyde, wherein the molar proportions of the reactants are in a ratio of from about A to 6 mols of chloralz'l mol of pentaerythritolzabout 6 to 1 mols of formaldehyde.

11. Dimensionally stable textile materials containing cellulosic fibers cross-linked with from about 1% to 30%, dry weight based on the dry weight of the textile materials, of a textile treating composition comprising a reaction product of chloral, pentaerythritol and formaldehyde, wherein the molar proportions of the reactants are in a ratio of from about A to 3% mols of chloralzl mol of pentaerythritohabout 3% to 1 mols of formaldehyde.

12. Dimensionally stable textile materials containing cellulosic fibers cross-linked with from about 1% to 30%, dry weight based on the dry weight of the textile materials, olf a textile treating composition comprising a re action product of chloral, pentaerythritol and formaldehyde, wherein the molar proportions of the reactants are in a ratio of from about A to 1% mols of chloralzl mol of pentaerythritolzabout 3% to 2 /2 mols of formaldehyde.

13. Dirnensiorrally stable textile materials containing cellulosic fibers cross-linked with from about 5% to 25% dry weight \based on the dry weight of the textile materials, of a textile treating composition comprising a reaction product of chloral, pentaerythritol and formaldehyde, wherein the molar proportions of the reactants rare in a ratio of from about A to 3% mols of chloralzl mol of pentaerythritol:3% to 1 mols of formaldehyde and the total mols of \chloral and formaldehyde per mol of pentaerythritol are not greater than 4.

14. Dimensionally stable textile materials containing cellulosic fibers cross-linked with from about 10% to 20%, dry weight based on the dry Weight of the textile materials, of a textile treating composition comprising a reaction product of chloral, pentaerythritol and formaldehyde, wherein the molar proportions of the reactants are in 'a ratio of from about A to 1 /2 mols of chloralzl mol of pentaerythritolzabout 3% to 2 /2 mols of formaldehyde and the total nrols of chloral and formaldehyde per mol of pentaerythritol are not greater than 4.

15. Dimensionally stalble textile materials containing cotton fibers cross-linked with from about 1% to 30%, dry weight based on the dry weight of the textile materials, of a textile treating composition comprising a reaction product of chloral, pentaerythritol and formaldehyde, wherein the molar proportions of the reactants are in a ratio of from about A; to 3% mols of chloralzl mol of pentaerythritohab out 3% to 1 mols of formaldehyde and the total mols of chloral and formaldehyde per H1101 of pentaerythritol are not greater than 4.

16. Dimensionally stable textile materials containing rayon fibers cross-linked with from about 1% to 30%, dry weight based on the dry weight of the textile materials, of a textile treating composition comprising a reaction product of chloral, pentaerythritol and formaldehyde, wherein the molar proportions of the reactants are in a ratio of from about A to 3% mols of chloral: 1 mol of pentaerythritolzaibout 3% to 1 mols of formaldehyde and the total mols of chloral and formaldehyde per mol of pentaerythritol are not greater than 4.

References Cited in the file of this patent UNITED STATES PATENTS 2,643,236 Kropa et al. June 23, 1953 2,784,237 Bruce Mar. 5, 1957 2,785,995 Kress Mar. 19. 1957 2,785,996 Kress Mar. 19, 1957 2,889,290 Capps June 2, 1959 

4. A METHOD OF TREATING TEXTILE MATERIALS CONTAINING CELLULOSIC FIBERS TO RENDER THE TEXTILE MATERIALS DIMENSIONALLY STABLE AFTER WASHING WHICH COMPRISES: APPLYING TO SAID TEXTILE MATERIALS FROM ABOUT 50% TO ABOUT 200% WET PICK-UP WEIGHT, BASED ON THE DRY WEIGHT OF THE TEXTILE MATERIALS, OF AN AQUEOUS SOLUTION COMPRISING FROM ABOUT 2% TO ABOUT 25% BY WEIGHT OF A REACTION PRODUCT OF CHLORAL, PENTAERYTHRITOL AND FORMALDEHYDE WHEREIN THE MOLAR PROPORTIONS OF THE REACTANTS ARE IN THE RATIO OF FROM ABOUT 1/4 TO 6 MOLS OF CHLORAL :1 MOL OF PENTAERYTHRITOL: ABOUT 6 TO 1/4 MOLS OF FORMALDEHYDE; AND DRYING SAID TREATED TEXTILE MATERIALS WHEREBY FROM ABOUT 1% TO ABOUT; 305, DRY WEIGHT, BASED ON THE DRY WEIGHT OF THE TEXTILE MATERIAL, REMAINS THEREON. 